CN101864163A - Preparation method of composite proton exchange membrane - Google Patents
Preparation method of composite proton exchange membrane Download PDFInfo
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- CN101864163A CN101864163A CN201010195372A CN201010195372A CN101864163A CN 101864163 A CN101864163 A CN 101864163A CN 201010195372 A CN201010195372 A CN 201010195372A CN 201010195372 A CN201010195372 A CN 201010195372A CN 101864163 A CN101864163 A CN 101864163A
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a preparation method of a composite proton exchange membrane, comprising the following steps of: sulfonating, preparing a sulfonated polyether ether ketone solution; preparing polyaniline filter liquid, preparing membrane preparing liquid, casting to form a membrane, and the like. The composite membrane is prepared by using SPEEK (sulfonated polyether ether ketone) as a basal body and PANI (Polyaniline) and HPA (Heteropoly acid) as dopants, a material source is wide and does not need to be imported, a preparation process is simple, and used instruments are simple, thereby the cost of the membrane is reduced. A hydrogen bond formed by PANI and SPEEK is used for avoiding the swelling of the SPEEK and reducing methanol penetration, and the proton conductivity of the composite membrane is improved by the HPA. By changing the composition and the ratio between an alkaline polymer and a proton conductor, the novel PEM (proton exchange membrane) reaches optimum balance among high proton conductivity, low methanol penetration and low HPA dropout rate, the proton conductivity reaches 10-2S/cm, the methanol penetration rate of the composite proton exchange membrane is a half lower than that of an Nafion 117 membrane, and the HPA wastage rate does not reach 5 percent.
Description
Technical field:
The present invention relates to a kind of preparation method of proton exchange membrane.
Background technology:
Proton exchange membrane (Proton exchange membrane, PEM) be Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cell, PEMFC) and directly one of core component of alcohol fuel battery (comprising DMFC and DEFC), its effect is: (1) separates anode and negative electrode, stops fuel and air (oxygen) directly to mix chemical reaction takes place; (2) proton conducting, proton conductivity are high more, and the internal resistance of film is more little, and the efficient of fuel cell is high more; (3) electrical insulator stops electronics to conduct in film, and by outside line road direction cathode flow, it is for people to use to produce foreign current by anode for electronics.Usually, fuel cell must satisfy following requirement with the PEM material: (1) low cost; (2) high proton conductivity; (3) good mechanical intensity (anti-swelling) and dimensional stability; (4) You Yi chemical stability and electrochemical stability; (5) very low gas or methanol permeability; (6) with the catalyst layer coupling; (7) life-time service is stable.
At present, Nafion series perfluoro sulfonic acid membrane has been obtained successful Application in PEMFC.This class material has higher proton conductivity, good mechanical intensity, excellent chemistry and advantages such as electrochemical stability and sufficiently long work-ing life.But it still exists some shortcomings: (1) requires height to temperature and water content, and its optimal working temp is 70 ℃～90 ℃, surpasses this temperature its water content is sharply reduced, and proton conductivity descends rapidly; (2) poor to the selection trafficability characteristic of first alcohol and water, alcohol-rejecting ability is poor, and the methyl alcohol more than 40% can see through this film in use, and this has just reduced battery performance and fuel availability, be not suitable for use in direct methanol fuel cell (Directmethanol fuel cell, PEM DMFC).The PEM that is used for DMFC is varied, and the DMFC that people developed so far is still lower with the proton conductivity of PEM, or methanol permeability is still higher, or cost is also expensive, thus the practical application that does not also reach DMFC.In order to overcome the shortcoming of existing P EM, be necessary the PEM of the high performance DMFC of being applicable to of developing low-cost.
Sulfonated polyether-ether-ketone (Sulfonated polyether ether ketone, SPEEK) film has good chemical stability, high-temperature stability and higher specific conductivity, and its hydrophilic channel is narrower than Nafion film, be unfavorable for that methyl alcohol passes through, this distinctive microtexture also makes its alcohol-rejecting ability be better than the Nafion film, has shown good prospects for application aspect DMFC.But (the degree of sulfonation DS) has much relations with use temperature for the performance of SPEEK film and its sulfonation degree.When DS and temperature all when higher, the SPEEK film has good proton conductivity, but its alcohol-rejecting ability is poor, and the serious even dissolving of its swelling in methanol aqueous solution; When DS and temperature were low, the SPEEK film had alcohol-rejecting ability preferably, but its proton conductivity is poor.Cai Yuquan etc. are in " polymer material science and engineering " (2007,23 (1): deliver " research that DMFC uses sulfonated polyether-ether-ketone/polyaniline commixed type proton exchange membrane " literary composition 246-249), they are with polyaniline (Polyaniline, PANI) add among the SPEEK, the hydrogen bond that utilizes the acid sulfonic group of the alkaline amido of PANI and SPEEK to take place to interact to form suppresses the swelling of SPEEK, though this can play the pure purpose of resistance, because the sulfonic group reduced number, proton conductivity reduces; Xue Song etc. are at " polymer journal " (2006, (9): deliver " conduction of sulfonated polyether-ether-ketone/phospho-wolframic acid composite membrane and methanol crossover performance " literary composition 1083-1087), they will have phospho-wolframic acid (the Phosphotungstic acid of high proton specific conductivity, PWA) join among the SPEEK, the proton conductivity of composite membrane has improved, but the problem that PWA runs off occurred, this has just influenced the performance of PEM.
Zhou Zhentao equals to disclose in 2007 preparation method's (publication number: CN101188301) of a kind of DMFC usefulness PEM.This method at first adds polyether-ether-ketone dense H
2SO
4In carry out sulfonation reaction and obtain SPEEK; Then SPEEK is dissolved in the organic solvent, add N, N '-carbonyl dimidazoles adds coupling agent stirring reaction 1.5h～4h after stirring 1h～3h, add inorganic crosslinking agent again 50 ℃～80 ℃ reactions down, add proton conductor then and continue under this temperature, to react the mixing solutions that obtains sulfonated polyether-ether-ketone/inorganic crosslinking agent/proton conductor; At last with the mixture solution film forming of sulfonated polyether-ether-ketone/inorganic crosslinking agent/proton conductor, drying, demoulding promptly obtains DMFC PEM.Though this film cost is low, water resisting swelling behavior is good under the features good methanol diffusion resistance, proton conductivity height, comparatively high temps.But technology is comparatively complicated, does not consider N, and N '-carbonyl dimidazoles and coupling agent are to the influence of film properties.
Utilize the advantage of SPEEK film, select suitable multi-element doping thing that SPEEK is carried out doping vario-property, regulate the proportioning between them, solve the proton conductivity of SPEEK proton exchange membrane and the contradiction between the alcohol-rejecting ability, make it both have good proton conductive, having alcohol-rejecting ability preferably again, then is the important directions of DMFC with the research of SPEEK proton exchange membrane.
Summary of the invention:
The object of the present invention is to provide a kind of preparation method of compound proton exchange membrane of the methanol crossover problem that can effectively solve direct methanol fuel cell.
Technical solution of the present invention is:
A kind of preparation method of compound proton exchange membrane is characterized in that: comprise the following steps:
(1) sulfonation:,, place 95%～98% dense H then with exsiccant polyether-ether-ketone powder with polyether-ether-ketone powder drying treatment
2SO
4In, the two ratio is 1g: 20～30mL, heated and stirred, behind reaction 2h～3h reaction solution is poured in the mixture of ice and water of 5 times of volumes at least, after the stirring, standing over night, filter out settled polymkeric substance, again repeatedly, near neutral, obtain sulfonation degree after the drying and be 50%～70% sulfonated polyether-ether-ketone up to the pH of solution value with deionized water wash;
(2) preparation sulfonated polyether-ether-ketone solution: with above-mentioned sulfonation degree is that 50%～70% sulfonated polyether-ether-ketone is dissolved in the N-methyl pyrrole network alkane ketone, is made into the sulfonated polyether-ether-ketone mass percent and is 10% sulfonated polyether-ether-ketone solution.
(3) preparation polyaniline filtrate: polyaniline is joined in the N-methyl pyrrole network alkane ketone, and stirring at room filters out undissolved polyaniline, and the polyaniline filtrate that obtains is stand-by; Take by weighing part filtrate, after the drying, the quality of the dry thing of weighing, the content of polyaniline in the calculating filtrate;
(4) preparation preparation liquid: according to sulfonation degree is that 50%～70% sulfonated polyether-ether-ketone is 50%～90% mass percent, polyaniline 5%～25% mass percent, the prescription requirement of heteropolyacid 5%～25% mass percent, the sulfonated polyether-ether-ketone solution that calculating and weighing step (2) obtain, polyaniline filtrate and the heteropolyacid that step (3) obtains, the three is mixed, stir, obtain the preparation liquid of proton exchange membrane.
(5) casting film-forming: in the sheet glass pond, 30 ℃ of dryings lose flowability preparation liquid with above-mentioned preparation liquid curtain coating, at 100 ℃ vacuum drying oven inner drying, naturally cool to room temperature at last, soak in deionized water, take off, promptly obtain proton exchange membrane.
(Heteropoly acid HPA) is phospho-wolframic acid, phospho-molybdic acid or silicotungstic acid etc. to described heteropolyacid.
The pH value of described solution is meant that near neutrality the pH value of solution is 6.5～7.5.
It is dry 10h in 100 ℃ of vacuum drying ovens that the middle polyether-ether-ketone powder of step (1) carries out drying; The temperature of heated and stirred is 60 ℃ in the step (1).
The mixture of ice and water of at least 5 times of volumes described in the step (1) is meant the mixture of ice and water of 5～10 times of volumes.
The present invention is matrix with SPEEK, be the composite membrane of hotchpotch preparation with PANI and HPA, material source is extensive, does not need import, and preparation technology is simple, used instrument is simple, has reduced the cost of film.The hydrogen bond that forms with PANI and SPEEK solves the swelling of SPEEK, reduces methanol crossover, reduces the HPA turnover rate, improves the proton conductivity of composite membrane with HPA.By changing the composition proportioning between alkaline polymer and the proton conductor, make new PE M between high proton specific conductivity, low methanol crossover and low HPA turnover rate, arrive best balance, proton conductivity reaches 10
-2S/cm, methanol permeability is at half than Nafion 117 films, and the HPA turnover rate is less than 5%.
The proton exchange membrane of the present invention's preparation has solved the methanol crossover problem when the Nafion film is used for DMFC, and proton conductivity does not reduce yet, and has satisfied the requirement of DMFC with PEM.
The proton exchange membrane of the present invention's preparation both can be used for direct methanol fuel cell, also can be used for alcohol fuel batteries such as direct alcohol fuel cell.
The invention will be further described below in conjunction with embodiment.
Embodiment:
Embodiment 1:
A kind of preparation method of compound proton exchange membrane comprises the following steps:
(1) sulfonation to get rid of moisture, takes by weighing the polyether-ether-ketone powder with polyether-ether-ketone powder dry 10h in 100 ℃ of vacuum drying ovens then, places 95%～98% dense H
2SO
4In, the two ratio is 1g: 20～30mL, 60 ℃ of following heated and stirred, behind reaction 2h～3h reaction solution is slowly poured in the mixture of ice and water of 5 times of volumes (5～10 times) at least, behind the stirring at room 1h, standing over night filters out settled polymkeric substance, again repeatedly, up to the pH of solution value approaching neutral (6.5～7.5) with deionized water wash.60 ℃ obtain down DS behind the dry 24h is 50%～70% SPEEK solid.
(2) preparation SPEEK solution is that 50%～70% SPEEK solid is dissolved in the N-methyl pyrrole network alkane ketone (NMP) with DS, is made into mass percent and is 10% sulfonation degree and be 50%～70% SPEEK solution.
(3) preparation PANI filtrate joins PANI among the NMP, and stirring at room 24h is dissolved among the NMP PANI as much as possible, filters out undissolved PANI.Take by weighing the filtrate of 10g～20g, behind 60 ℃ of following dry 48h, the quality of the dry thing of weighing (powder) is to calculate the content of PANI in the filtrate.
(4) the preparation preparation liquid is that 50%～70% SPEEK solid is 50% mass percent according to sulfonation degree, PANI powder 25% mass percent, the prescription requirement of HPA particle 25% mass percent, the sulfonated polyether-ether-ketone solution that calculating and weighing step (2) obtain, polyaniline filtrate and the heteropolyacid that step (3) obtains, the three is mixed, stirring at room 1.5h so just obtains the preparation liquid of proton exchange membrane.HPA is the heteropolyacid with high proton specific conductivity, and HPA is phospho-wolframic acid, phospho-molybdic acid or silicotungstic acid etc.
(5) in the sheet glass pond, 30 ℃ of dryings lose flowability preparation liquid to casting film-forming with above-mentioned preparation liquid curtain coating, at 100 ℃ vacuum drying oven inner drying 12h, naturally cool to room temperature at last, soak in deionized water, take off, promptly obtain proton exchange membrane.The proton conductivity of proton exchange membrane is 1.5 * 10
-2S/cm, methanol permeability are 1 * 10
-7Cm
2/ s, the heteropolyacid turnover rate is 3.0%.
Embodiment 2:
The formula rate of step (4) is: sulfonation degree is that 50%～70% SPEEK solid is 60% mass percent, PANI powder 15% mass percent, HPA particle 25% mass percent; All the other are with embodiment 1.The proton conductivity of proton exchange membrane is 2 * 10
-2S/cm, methanol permeability are 1.8 * 10
-8Cm
2/ s, the heteropolyacid turnover rate is 2.7%.
Embodiment 3:
The formula rate of step (4) is: sulfonation degree is that 50%～70% SPEEK solid is 70% mass percent, PANI powder 10% mass percent, HPA particle 20% mass percent; All the other are with embodiment 1.The proton conductivity of proton exchange membrane is 2.4 * 10
-2S/cm, methanol permeability are 2.5 * 10
-7Cm
2/ s, the heteropolyacid turnover rate is 2.8%.
Embodiment 4:
The formula rate of step (4) is: sulfonation degree is that 50%～70% SPEEK solid is 80% mass percent, PANI powder 10% mass percent, HPA particle 10% mass percent; All the other are with embodiment 1.The proton conductivity of proton exchange membrane is 1.5 * 10
-2S/cm, methanol permeability are 2.8 * 10
-7Cm
2/ s, the heteropolyacid turnover rate is 1.5%.
Embodiment 5:
The formula rate of step (4) is: sulfonation degree is that 50%～70% SPEEK solid is 90% mass percent, PANI powder 5% mass percent, HPA particle 5% mass percent; All the other are with embodiment 1.The proton conductivity of proton exchange membrane is 2 * 10
-2S/cm, methanol permeability are 1 * 10
-7Cm
2/ s, the heteropolyacid turnover rate is 1.5%.
Claims (5)
1. the preparation method of a compound proton exchange membrane is characterized in that: comprise the following steps:
(1) sulfonation:,, place 95%～98% dense H then with exsiccant polyether-ether-ketone powder with polyether-ether-ketone powder drying treatment
2SO
4In, the two ratio is 1g: 20～30mL, heated and stirred, behind reaction 2h～3h reaction solution is poured in the mixture of ice and water of 5 times of volumes at least, after the stirring, standing over night, filter out settled polymkeric substance, again repeatedly, near neutral, obtain sulfonation degree after the drying and be 50%～70% sulfonated polyether-ether-ketone up to the pH of solution value with deionized water wash;
(2) preparation sulfonated polyether-ether-ketone solution: with above-mentioned sulfonation degree is that 50%～70% sulfonated polyether-ether-ketone is dissolved in the N-methyl pyrrole network alkane ketone, is made into the sulfonated polyether-ether-ketone mass percent and is 10% sulfonated polyether-ether-ketone solution.
(3) preparation polyaniline filtrate: polyaniline is joined in the N-methyl pyrrole network alkane ketone, and stirring at room filters out undissolved polyaniline, and the polyaniline filtrate that obtains is stand-by; Take by weighing part filtrate, after the drying, the quality of the dry thing of weighing, the content of polyaniline in the calculating filtrate;
(4) preparation preparation liquid: according to sulfonation degree is that 50%～70% sulfonated polyether-ether-ketone is 50%～90% mass percent, polyaniline 5%～25% mass percent, the prescription requirement of heteropolyacid 5%～25% mass percent, the sulfonated polyether-ether-ketone solution that calculating and weighing step (2) obtain, polyaniline filtrate and the heteropolyacid that step (3) obtains, the three is mixed, stir, obtain the preparation liquid of proton exchange membrane.
(5) casting film-forming: in the sheet glass pond, 30 ℃ of dryings lose flowability preparation liquid with above-mentioned preparation liquid curtain coating, at 100 ℃ vacuum drying oven inner drying, naturally cool to room temperature at last, soak in deionized water, take off, promptly obtain proton exchange membrane.
2. the preparation method of compound proton exchange membrane according to claim 1, it is characterized in that: described heteropolyacid is phospho-wolframic acid, phospho-molybdic acid or silicotungstic acid.
3. the preparation method of compound proton exchange membrane according to claim 1 and 2, it is characterized in that: the pH value of described solution is meant that near neutrality the pH value of solution is 6.5～7.5.
4. the preparation method of compound proton exchange membrane according to claim 1 and 2 is characterized in that: to carry out drying be dry 10h in 100 ℃ of vacuum drying ovens to the polyether-ether-ketone powder in the step (1); The temperature of heated and stirred is 60 ℃ in the step (1).
5. the preparation method of compound proton exchange membrane according to claim 1 and 2 is characterized in that: the mixture of ice and water of at least 5 times of volumes described in the step (1) is meant the mixture of ice and water of 5～10 times of volumes.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329432A (en) * | 2011-07-26 | 2012-01-25 | 中国科学院长春应用化学研究所 | Method for preparing sulfonic acid polymer proton exchange membrane |
| CN103013039A (en) * | 2012-09-11 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Sulfonated aromatic polymer/side-chain sulfimide-group-containing aromatic polymer blended ion exchange membrane, and preparation method and applications thereof |
| CN104091907A (en) * | 2014-06-12 | 2014-10-08 | 苏州经贸职业技术学院 | Fuel cell membrane material and preparation method thereof |
| CN104411774A (en) * | 2012-06-18 | 2015-03-11 | 国立大学法人熊本大学 | Composite of polymer and tungstic acid and/or molybdic acid |
| CN105680077A (en) * | 2016-01-13 | 2016-06-15 | 山东星火科学技术研究院 | Proton exchange membrane |
| WO2016124052A1 (en) * | 2015-02-05 | 2016-08-11 | 成都新柯力化工科技有限公司 | Proton exchange membrane for fuel cells and preparation method therefor |
| CN108649244A (en) * | 2018-05-10 | 2018-10-12 | 长沙理工大学 | Preparation method of SPEEK/lignin composite diaphragm |
| CN109065925A (en) * | 2018-07-23 | 2018-12-21 | 中国科学院金属研究所 | A kind of Iron/chromium Redox Flow Cell non-fluorine both sexes composite membrane and preparation method |
| CN109585872A (en) * | 2018-10-24 | 2019-04-05 | 长沙理工大学 | Preparation method of SPEEK diaphragm applied to zinc-iron flow battery |
| CN109585892A (en) * | 2018-10-24 | 2019-04-05 | 长沙理工大学 | Preparation method of SPEEK/MCM composite diaphragm |
| CN109912928A (en) * | 2019-03-18 | 2019-06-21 | 山东星火科学技术研究院 | The preparation method of sulfonated polyether-ether-ketone and phosphotungstic acid composite membrane |
| CN110649301A (en) * | 2019-10-31 | 2020-01-03 | 宇石能源(南通)有限公司 | Preparation method of composite proton exchange membrane |
| CN115548398A (en) * | 2022-11-08 | 2022-12-30 | 安徽理工大学 | Preparation method of sulfonated polyether ether ketone, silicotungstic acid and ionic liquid doped modified polyvinyl chloride-based proton exchange membrane |
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| CN102838777B (en) * | 2012-08-23 | 2014-11-26 | 南通大学 | Recovery method of sulfonated polyether ether ketone (SPEEK) / polyaniline (PANI) / propylene glycol monomethyl acetate (PMA) composite proton exchange membrane |
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| CN102329432A (en) * | 2011-07-26 | 2012-01-25 | 中国科学院长春应用化学研究所 | Method for preparing sulfonic acid polymer proton exchange membrane |
| CN104411774A (en) * | 2012-06-18 | 2015-03-11 | 国立大学法人熊本大学 | Composite of polymer and tungstic acid and/or molybdic acid |
| CN103013039A (en) * | 2012-09-11 | 2013-04-03 | 中国科学院宁波材料技术与工程研究所 | Sulfonated aromatic polymer/side-chain sulfimide-group-containing aromatic polymer blended ion exchange membrane, and preparation method and applications thereof |
| CN103013039B (en) * | 2012-09-11 | 2014-10-08 | 中国科学院宁波材料技术与工程研究所 | Sulfonated aromatic polymer/side-chain sulfimide-group-containing aromatic polymer blended ion exchange membrane, and preparation method and applications thereof |
| CN104091907A (en) * | 2014-06-12 | 2014-10-08 | 苏州经贸职业技术学院 | Fuel cell membrane material and preparation method thereof |
| WO2016124052A1 (en) * | 2015-02-05 | 2016-08-11 | 成都新柯力化工科技有限公司 | Proton exchange membrane for fuel cells and preparation method therefor |
| CN105680077A (en) * | 2016-01-13 | 2016-06-15 | 山东星火科学技术研究院 | Proton exchange membrane |
| CN108649244B (en) * | 2018-05-10 | 2020-11-17 | 长沙理工大学 | Preparation method of SPEEK/lignin composite diaphragm |
| CN108649244A (en) * | 2018-05-10 | 2018-10-12 | 长沙理工大学 | Preparation method of SPEEK/lignin composite diaphragm |
| CN109065925A (en) * | 2018-07-23 | 2018-12-21 | 中国科学院金属研究所 | A kind of Iron/chromium Redox Flow Cell non-fluorine both sexes composite membrane and preparation method |
| CN109065925B (en) * | 2018-07-23 | 2021-07-23 | 中国科学院金属研究所 | Non-fluorine amphoteric composite membrane for iron-chromium redox flow battery and preparation method |
| CN109585892A (en) * | 2018-10-24 | 2019-04-05 | 长沙理工大学 | Preparation method of SPEEK/MCM composite diaphragm |
| CN109585872A (en) * | 2018-10-24 | 2019-04-05 | 长沙理工大学 | Preparation method of SPEEK diaphragm applied to zinc-iron flow battery |
| CN109585892B (en) * | 2018-10-24 | 2021-03-23 | 长沙理工大学 | Preparation method of SPEEK/MCM composite diaphragm |
| CN109912928A (en) * | 2019-03-18 | 2019-06-21 | 山东星火科学技术研究院 | The preparation method of sulfonated polyether-ether-ketone and phosphotungstic acid composite membrane |
| CN110649301A (en) * | 2019-10-31 | 2020-01-03 | 宇石能源(南通)有限公司 | Preparation method of composite proton exchange membrane |
| CN110649301B (en) * | 2019-10-31 | 2022-06-03 | 宇石能源(南通)有限公司 | Preparation method of composite proton exchange membrane |
| CN115548398A (en) * | 2022-11-08 | 2022-12-30 | 安徽理工大学 | Preparation method of sulfonated polyether ether ketone, silicotungstic acid and ionic liquid doped modified polyvinyl chloride-based proton exchange membrane |
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